HU213638B - Method for producing herbicidal granular compositions - Google Patents

Abstract

The invention relates to a method of producing granular mixtures which contain herbicides known per se, the activator used being a solid composition in which the activator ingredients are either impregnated into and/or mixed with a carrier material.

Description

(57) EXTRAS

The present invention relates to a process for the preparation of a granular herbicidal composition, wherein the herbicide is methyl [3- (m-tolylcarbamoyloxy) phenyl] carbamate or ethyl [3- (phenylcarbamoyloxy) phenyl]. carbamate and surfactants and / or oils as an activator component, which are mixed with a solid carrier to form a solid activator composition.

According to the invention, the process is carried out by:

(a) preparing a granulate formulation containing the herbicide and then coating the granulate with a solid activator formulation; or

(b) preparing a granulate containing the solid activator composition and coating the granulate with a solid phase containing the herbicide; or

c) preparing a granulate composition comprising a herbicidal active ingredient and a granulation composition comprising an activator and mixing the two granulation compositions.

Scope of the description: 12 pages (including 1 page figure)

HU 213 638 B

HU 213 638 Β

FIELD OF THE INVENTION The present invention relates to granular herbicidal compositions which contain carbamoyloxyphenylcarbamates as active ingredients, and also contain surfactants, suspending agents, inert carriers and optionally other auxiliary components such as stabilizers, antifoams, coloring agents and preservatives. Although these active substances are insoluble in water, they must be sprayed in water diluted in water on the areas planted with the plant in order to exert an effect on the foliage. To solve this problem, a water dispersible granulate was prepared which, when diluted with water, gave a homogeneous suspension which did not cause plugging in the sprayer.

Carbamoyloxyphenylcarbamate herbicides are generally prepared in the form of a concentrate in the form of an emulsion in which the active ingredient is dissolved in organic solvents and is thus suitable for forming an emulsion in water. However, such formulations are toxic and flammable due to the use of organic solvents and it is very difficult to form a non-crystallizing emulsion of the product by mixing with water. Crystallization is typical for methyl [3- (tolylcarbamoyloxy) phenyl] carbamate.

Formulations in which the active ingredient is in an undissolved form are preferred, since problems of toxicity, flammability, packaging and storage can be avoided. This is because, especially when herbicides are applied to foliage, it is necessary to have the appropriate penetration and / or change of position characteristics in order for the active ingredient to have a biologically active effect. Degradation solutions resulting from hydrolysis may also be a common drawback. When the active ingredient is present in a molecular form in a true liquid, it is able to pass through the wax and vegetation layers and thus be more effective than the solid particle form. To this end, insoluble particles or active ingredients of this type should be ground to the finest powder possible and their penetration into the plant and their ability to change position should be promoted with oils, organic solvents and surfactants. In particular, carbamoyloxyphenylcarbamates are active ingredients for which it is inevitable that large amounts of the above excipients will be required to achieve adequate biological efficacy. For the above materials, air-jet and slurry mills are used to comminute the active ingredient to a maximum fine powder, preferably having a size of 1-5 micrometers. This milling is carried out in order to obtain a suitable biological activity or to form a stable suspension by dispersing the granulate in water.

The active ingredient in solid form may be present in a water-dilutable preparation or as a liquid suspension concentrate or a water-dispersible granular product. The disadvantage of a liquid product is often that it is difficult to store, difficult to handle because of its high viscosity and because the containers cannot be emptied completely. The latter disadvantage is significant from the environmental point of view, since the used containers have to be disposed of somewhere. These problems can be avoided by using liquid dispersible solid granule forms. In addition, the granular product can be packaged in materials, such as paper, which are less harmful to the environment and easier to dispose of used packaging material.

In addition to the chemical stability of the active ingredients, water-dispersible granules have the essential property of being highly dispersible in water and having a suitable cohesive effect, so that no harmful fumes are formed during storage and handling, and the granules are free flowing and do not stick. In order to obtain granules of this type, the granules may contain, in addition to a water-insoluble carrier, dispersing, suspending, wetting, preserving, antifoaming and anti-caking agents.

Carbamoyloxyphenylcarbamates, the most important of which is methyl [3- (m-tolylcarbamoyloxy) -phenyl] -carbamate, are commonly known as phenmedipham and ethyl- [3- (phenyl) carbamates. carbamoyloxy-phenyl] -carbamate, trivially desmedipham (BP 679,283), a compound of formula (I) wherein R 1 and R 6 are as defined herein. is methyl or R 1 is hydrogen and R ₂ is ethyl - selective and highly effective herbicides. These active ingredients may be used singly or in admixture and / or may be used in admixture with other herbicidal active substances, in particular for weed control, in sugar beet production.

Generally, the above active compounds are marketed as emulsion concentrates. However, in the preparation of herbicidal compositions, the use of organic solvents is avoided, and since phenmedipham crystallizes when diluted with water, it has become necessary to obtain a water dispersible granule form of the above active ingredients. It is already known in the art that water-dispersible granule forms from herbicides (US 3,920,442) and dispersible triazine herbicide granules containing surfactants have been described which improve the crystallization characteristics (US 4,197,112) and materials (EP 201,417). The disadvantage of commercially available dispersible carbamoyloxyphenyl carbamates is that it is very difficult to assure proper biological efficacy of the product because the amount of liquid oil and / or surfactant required is very high in relation to the active ingredient (about 1: 1) and therefore not economically applicable to plant protection.

Thus, it is known that good biological efficacy can be achieved by the use of water-dispersible granules of certain herbicides, but carbamoyloxy

HU 213 638 Β

in the case of phenylcarbamates, this process has so far failed to achieve the desired efficacy.

Surprisingly, our studies have found that water-dispersible granular products containing carbamoyloxyphenylcarbamate can be obtained by not only providing the above-mentioned advantageous properties in the granular product, but also substantially improving them by providing a granular product or tablet. A product of Form I is prepared by impregnating the activator into a carrier which is then uniformly distributed or applied as a layer to the surface of the granulate or tablet or applied as a core to the inside of the granule or tablet. Alternatively, separate granules or tablets may be prepared with the aid of a liquid activator and carrier. These prepared granules are mixed with the active ingredient-containing granulate and packaged in the same container to evenly mix these granules. Thus, a uniform product is obtained or the two types of granules mentioned above can be dispersed separately in the container. A separate tablet formulation may be combined with the active ingredient granule or tablet formulation to form a combined formulation for use.

The present invention therefore relates to a process for the preparation of a herbicidal composition in the form of granules comprising as active ingredient methyl [3- (m-tolylcarbamoyloxy) phenyl] carbamate or ethyl [3- (phenylcarbamoyloxy) phenyl] carbamate. and containing, as activator component, surfactants and / or oils, wherein the activator component is mixed with a solid carrier to form a solid activator composition to form a herbicidal composition comprising two separate solid phases and the product is swallowed by the following procedure.

(a) preparing a granulate composition containing the herbicidal active ingredient and coating the granulate with a solid activator composition; or

b) preparing a granulate comprising a solid activator composition and coating the granulate with a solid phase containing the herbicidal agent; or

c) first preparing a granulate composition containing the herbicidal active ingredient, second preparing a granule containing a solid activator composition and mixing the first and second granules.

When an impregnated activator is used in a carrier, the biological activity of the solid carbamoyloxyphenylcarbamate can be further enhanced compared to the use of a non-impregnated activator. This phenomenon was also observed in greenhouse and field tests.

Organic materials capable of absorbing large amounts of oily material which are of natural origin, such as silica-based materials, alumina-based materials, attapulgite, montmorillonite, microparticulate materials, diatomite, bentonite, talc, kaolin, potassium ash, gypsum and water-insoluble or water-soluble salts.

Carriers may also include porous organic materials of natural origin, such as shredded wood or corn cobs, shredded coconut or almond shells, shredded olive shells, bran, cellulose, starch and alginates, or porous structures originally modified from polymeric materials, e.g. lignin derivatives, cellulose derivatives, starch derivatives and cyclodextrins, or synthetic polymers such as polyacrylates, polyacrylamides, polyvinyl derivatives, maleic acid polymers, polyurea, polylactides and glycolic acid polymers may be used.

The activator may be incorporated into the carrier by coating the impregnated particles with a polymer which may be polyvinyl alcohol or a sugar or sugar alcohol based material such as lactose, CMC and sorbitol. In this way, the release rate of the activator material can also be controlled.

The liquid activator can also be used and encapsulated, which can then be used as part of a granular material. Encapsulation methods are known in the art. The strength of the granules and their resistance to abrasion can also be modified by the use of coatings. On the other hand, the flowability of the product can also be improved by coating materials.

For the purpose of the present invention, it is not relevant that the activator contains surfactants and / or oil, since the main purpose of its granulation is to improve the biological effect of the product.

The ratio of activator in the granular product is generally from 1 to 80% by weight, preferably from 0.5 to 5 times the amount of carbamoyloxyphenylcarbamate in the final product.

The activator may be solid or liquid at 20 ° C, in which case it may be impregnated with the carrier or mixed with the mixture to be granulated. Alternatively, the activator may be bonded to the product by some other method or impregnated into the product after granulation.

The activator may contain anionic, cationic, nonionic or amphoteric surfactants or such materials in combination with a mineral oil, vegetable oil or animal oil. The ratio of surfactants in the activator is 2-100% by weight, preferably 50-100% by weight. The proportion of oil in the above cases may be 0.98% by weight, preferably 0-501%.

The anionic surfactants include alkyl sulfonates, alkyl aryl sulfonates, sulfate ethers, fatty alcohol sulfates, sulfate ester sulfocarboxylic acids and derivatives thereof, alkyl glycerol ether sulfonates, sulfo esters and sulfonamides and , bile acids and their salts.

The cationic surfactants may be alkylamines or alkylarylamines, alkyl- or alkylaryl-imidazolines, and alkylaminoamides.

Nonionic surfactants include fatty alcohol ethoxylates, fatty acid ethoxylates, alkylaryl ethoxylates,

EN 213 638 Β Alkyl sugar ethoxylates or alkyl sugar alcohol ethoxylates, alkylamine or alkylarylamine polyglycol ethers, fatty acid amide derivatives, fatty acid diethanolamines or poly diethanolamides , derivatives of mono-, di- and triglycerides, acetylene diols and silicone based surfactants.

Amphoteric surfactants may include alkyl and alkylaryl betaine derivatives, alkyl and alkylaryl (poly) glycine derivatives, alkylamide and alkylaryl amide carboxylates, and alkylamine and alkyl. -aryl-amine sulphonates. Surfactants containing fluorine may also be used.

The oily material may be a mineral oil which is preferably of low viscosity and thus easily impregnated in the carrier. In addition, the oil should be such that it does not significantly penetrate the crop. Most preferred are low-aromatic paraffin oils such as Neutral solvent 150, Exxon. The oily material may also be a vegetable oil or a hydrolytic product thereof, such as soybean oil or a mixture of soybean fatty acids, and the oil may further comprise phospholipids and sterols.

In addition, the oily material may be of animal origin, in which case the preferred oil will contain high levels of unsaturated fatty acids or such fatty acid glycerides.

It is a basic requirement that the active ingredient granulate or the active ingredient and the carrier material containing the activator, or the carrier granule or the active ingredient or activator granulate, be in a very finely divided form.

For example, the material may be ground in a dry state in an air-jet mill or in suspension in a pearl mill. It is essential that the solids have an average particle size of 10 µm and that the active ingredient preferably has a particle size of 5 µm (as measured by a Coulter apparatus) in order to achieve the appropriate biological activity.

Excipients may be added to the granulate to promote granulation formation, rehydration and rapid degradation, and dispersion of the granules when preparing a ready-to-use suspension, and materials that inhibit foaming of the ready-to-use solution. Since the active ingredient can be degraded in a ready-to-use basic solution, inorganic or organic pH adjusting agents, for example phosphoric or acid salts and citric acid, may be used to keep the pH of the solution used below 7, preferably 3, The value should be between 5 and 5.5.

Granulation excipients may be used in the granules, provided that the active ingredient and the activator are in the same granule, or mixtures of granules and activator granules containing the separate active ingredient can be used.

Additives that aid in the degradation of the granulate composition may be polymers such as polyvinylpyrrolidone and starch, and modified forms thereof, or salts such as ammonium sulfate or organic water-soluble compounds such as urea or gas release compounds such as carbonates. .

Additives that aid in granule suspension include those commonly used as dispersants, such as phenylsulfonates, alkylnaphthylsulfonates and polymerized naphthylsulfonates, polyacrylic acid forms and their salts, polyacrylamides, polyalkoxydiamines, ), poly (propylene oxide), polybutylene oxide, taurine derivatives and mixtures thereof, and sulphonated lignin derivatives. The dispersants are present in the granular product in an amount of 0.1 to 50% by weight, preferably 5 to 20% by weight.

Similar products may be used as excipients in the granulation aid, for example, polyethylene glycol, preferably in the range of from 1 to 20% by weight of the granulate containing the active ingredient to the component containing this activator.

The foaming of the spray release mixture may be controlled by the use of antifoams, which may be, for example, silica-based agents. Preferably, such antifoam additives are used in an amount of 0 to 0.5% by weight based on the amount of granular product.

Granulation can be carried out by methods known in the art, such as sheet granulation, spray drying (e.g. Niro), fluid bed granulation (e.g. Glatt and Schugi), blend granulation using a vertical mixer (e.g. Fielder) or late blender granulation (e.g. Forberg), extrusion granulation (e.g. Nica). ) or compact granulation (e.g., Bepex equipment) or centrifugal granulation (e.g., CF granulator, Freund Industrial Co) and spray bed granulation.

The activator material can be complimented into a water dispersible tablet, in which case its size may vary depending on the quality of the matrix. Commonly used tablet presses include rotary (Mansty) and eccentric tablet presses (Diaf).

In addition, one or two of the above methods may be used sequentially for granulation and tabletting purposes. The surface of the granulate may be cured mechanically, for example by rotating the granulate, for example using a Spheronizer (Nica) or by coating the granules using the appropriate coating materials mentioned above.

It is essential that the granular product is dried. The product may be dried either in a granulating device or in a separate device specifically designed for drying (e.g., in a fluid bed dryer). Preferably, the granulated product has a moisture content of less than 5%, most preferably less than 1%.

The size of the final product granulate may vary depending on the granulation process used and may be up to 3 mm or significantly larger when producing a water dispersible tablet form.

Of course, other active ingredients may also be combined with carbamoyloxylphenyl carbonates (e.g., phenmedipham and desmedipham) to provide the

EN 213 638 Β granular product. Other active ingredients include herbicides, herbicides, insecticides, and growth regulators.

Preferred herbicides are especially used in sugar beet cultivation such as etofumesate, metamitron, chloridazone, lenacil, pyridate, metolachlor, trichloroacetic acid, EPTC, quinmerac, cycloate, clopiralide, flur isocarbamide, propham, trifluralin, alloxydim sodium, setoxidime, diabate, fluazifop-butyl, triallate, dalapone or propaquizafop.

The compounds of the present invention can be applied after the crop has been sown after the crop has emerged, preferably several times during the growing season. The application rate is 0.1-1 kg / ha, depending on how many sprays are applied.

The following examples illustrate the process of the invention in more detail. The active substances of the above herbicide formulations, as well as the ingredient names of the following, are designated by their chemical names:

ethofumesate (±) -2-Ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulfonate methamitron 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one chloridazon 5-amino-4-chloro-2-phenyl-3 (2H) -one lenacil 3-cyclohexyl-1,5,6,7-tetrahydro-cyclopenta-2,4 (3H) -dione pyridate 6-Chloro-3-phenylpyridazin-4-yl S-octylthiocarbonate metolachlor 2-Chloro-6'-ethyl-N- (2-methoxy-1-methylethyl) acetotoluidide EPTC S-ethyl dipropylthiocarbamate quinmerac 7-Chloro-3-methyl-quinoline-8-carboxylic acid cycloate S-ethyl cyclohexyl (ethyl) thiocarbamate clopyralid 3,6-dichloro-2-pyridine-2-carboxylic acid fiuroxypyr 4-amino-3,5-dichloro-6-fluoro-2-pyridyl oxyacetate isourea N-isobutyl-2-oxoimidazolidine-1-carboxamide propham isopropylphenyl carbamate trifluralin a, a, a-trifluoro-2,6-dinitro-N, N-dip -propyl-p-toluidine alloxidine sodium methyl [(E) - (RS) -3- [1- (allyloxyimino) butyl-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-en] - carboxylate sethoxydim (±) - (EZ) -2- (1-Ethoxyimino-butyl) -5- - [2- (ethylthio) propyl] -3-hydroxy-cyclo- hex-2-enone diallate S- (2,3-dichloro-allyl) diisopropyl-(thio carbamate) fluazifop-butyl butyl {(RS) -2- [4- (5- (trifluoromethyl) -2-pyridyl) phenoxy] -propionate triallate S- (2,3,3-trichloro-allyl) diisopropyl- - (thiocarbamate) dalapon 2,2-dichloropropionic acid

propaquizafop [2- (isopropylideneaminooxy) ethyl] - (R) -2- [4- (6-chloroquinoxalin-2-yloxy) -phenoxy] -propionate

Goltix (BAYER AG) is a brand name for the metamitron granule formulation

SC Goltix (BAYER AG) is a trademark of Metamitron Suspension Concentrate

Betaflow is the trade name for Phenmedipham Suspension Concentrate (HOECHST-SCHEIZING

AGREVO) (DE)

Beta Compact is the brand name for Phenmedipham and Desmedipham Emulsion Concentrate (HOECHST-SCHEIZING

AGREVO) (DE

Example I

Separate granules of phenmedipham product can be prepared

from the raw material blend, which is . (% =% by weight) phenmedipham 80% lignosulfonates 7.4% phenyl sulfonates 7.0% diatomite 2.0% kaolin 3.6%

The crude products used in the preparation are pre-ground in an air-flow granulation mill (Alpine). The granulation is carried out by extrusion (Nice), whereby 10% by weight of water, based on the amount of the mixture, is mixed with the starting mixture. The openings in the matrix have a diameter of 1 mm. The extruded mixture is then cca. Cut into granules of 2 mm length, which are then spheronized in a Spheronizer. The product was dried in a fluid bed dryer. The product obtained is highly dispersible in water.

Suspendability is tested in an apparatus in which 1 g of product is dispersed in a 100 ml narrow-necked graduated test tube containing 100 ml of distilled water at 25 ° C. Once the granules have been wetted, the tube is rotated 30 times by 180 °. Subsequently, the precipitate formation and the amount thereof are examined after 1 min, 5 min and 10 min. For the above-mentioned granules, a precipitate precipitated 1 min after mixing, 0.05 ml, 0.05 ml after 5 minutes and 0.05 ml after 10 minutes.

The average particle size of the suspension measured with a Coulter LS 130 is 2 µm.

For purposes of comparison, the suspension characteristics of the commercial product Goltix were determined. The values obtained are as follows: 1 min / 0.01 ml; 5 min / 0.1 ml; and 10 min / 0.18 mL.

Example 2

A separate granulated phenmedipham product is prepared from a pre-ground mixture of crude product containing the following components:

(% =% by weight)

HU 213 638 Β Phenmedipham 89% Lignin sulfonate derivatives 7.2% Phenylsulfonate 3.6%

The mixture may be spray-granulated starting from a 50% suspension of a 5% aqueous mixture (Niro). The average particle size of the granulate depends on the size of the equipment. The granules are spherical. The suspension was determined by the above procedure and the following results were measured: 1 min / 0.15 ml; 5 min / 0.9 mL; 10 for 10 min / 1.2 ml. The suspension has an average particle size of 3 µm.

Example 3

A separate granulate phenmedipham product was prepared starting from the starting materials of Example 1 by plate granulation. During granulation, the mixture is moistened with 10% by weight of water based on the dry matter before granulation. Suspension test result: 1 min / 0.02 ml; 20 min / 0.15 mL; 10 min / 0.25 mL. The average particle size of the suspension is 3 µm.

Example 4

A separate granulate composition comprising an activator is prepared from a pre-ground carrier blend by plate granulation, wherein the pre-ground carrier blend comprises the following materials:

(% =% by weight)

hard acid (Zeothix 265) 30 (SIGMA-ALDRICH CO. GmbH) 85% ammonium sulfate 2% NaCI 2% lignosulfonates 2% phenyl sulfonates 5% 35

then impregnated in a 1: 1.5 ratio in activator solution (Mixture A), where Mixture A is

Teluk: alkyl sorbitol ethoxylate 42% fatty alcohol ethoxylate 21% 40 ethoxylated fatty acid esters 8% ethoxylated fatty acid phosphate esters 5% alkyl aryl sulfonic acid 5% alkylamine ethoxylate 4% paraffin 15% 45

The discrete granule composition containing the activator can then be mixed with the discrete granule mixture containing the active ingredients as described above to form a mixture or disperse the granules containing the discrete activator separately to form a container mixture.

The granules are slightly dispersible in water.

Example 5 55

A granulate product containing phenmedipham and an activator is prepared from the following raw material mixture:

(% = by weight) Phenmedipham 16.0% Lignin sulfonates 2.6% 60

phenyl sulfonates 5.5% urea 7.0% kaolin 5.5% diatomite 5.0% Mixture B 50.4% polyethylene glycol 8.0% Composition of mixture B: silica (precipitated) 37.5% bentonite 2.5% fatty alcohol ethoxylates 16.0% polyoxyethylene sorbitols 33.8% paraffin 5.1% alkylamine ethoxylates 5.1%

The mixture was subjected to plate granulation, which was heated to 70 ° C. The resulting granulate product is cooled to room temperature. The characteristics of the product suspension are medium.

Example 6

Phenmedipham and an activator-containing layered granular product are prepared from the following mixture:

(% = weight%) Phenmedipham lignin sulfonates Phenyl sulfonates Kaolin Diatomaceous polyethylene glycol

Mixture B

16.0%

2.7%

5.3%

15,5%

5.0%

5.0%

50.4% (as in Example 5)

Coating B is applied using a polyethylene glycol excipient to coat granules made from the above other raw materials. The granulation is carried out in a plate granulator at 70 ° C. The granulated product has medium suspension characteristics.

Example 7

Phenmedipham and an activator granulated

The product is prepared by extrusion process as follows nyersanyagkeverékből: (% =% by weight) phenmedifam 32.0% lignosulfonates 7.4% phenyl sulfonates 2.0% kaolin 1.1% diatomite 2.0% nafténszulfonátok 2.0% C mixture 50.0% Composition of mixture C: silica (precipitated) 34.0% phenyl sulfonates 0.8% ammonium sulfate 0.8% NaCI 1.6% lignosulfonates 0.8% naftilénszulfonátok 2.0% The mixture 60.0%

The result of the suspension test:

min / 0.15 mL; 5 min / 0.3 mL; 10 min / 0.4 mL.

HU 213 638 Β

Example 8

Granulated product containing phenmedipham and desmadifam

Preparing meats from the following mixture: (% =% by weight) phenmedipham 60.0% desmedipham 20.0% lignosulfonates 5.9% phenyl sulfonates 5.6% kaolin 4.0% diatomite 2.0%

Suspension characteristics of the granulated product: 1 min / 0.01 ml; 5 min / 0.02 mL; 10 min / 0.03 mL.

Example 9

Phenmedipham and ethofumesate-containing granulated product are prepared by a plate granulation process starting from the following mixture:

(% = by weight) Phenmedipham 32.0% Ethofumesate 40.0% Lignin sulfonates 6.0% Phenylsulfonates 5.0% Naphthenesulfonates 9.0% Bentonite 0.2% Urea 7.8%

Example 11

Granulated product containing phenmedipham and chlorideazone

two are prepared using plate granulation as follows starting with mixture: (% = by weight) Phenmedipham 25.0% chloridazon 50.0% lignosulfonates 5.9% phenyl sulfonates 5.6% diatomite 1.1% kaolin 12,4%

Suspension characteristics of the granulated product: 1 minute / 0.03 ml; 5 min / 0.10 mL; 10 min / 0.15 mL.

Example 11b

Phenmedipham and Chloridazone containing granules

prepared by plate granulation as follows starting with mixture: (% =% by weight) phenmedifam 20.0% chloridazon 60.0% ligniszulfonátok 5.9% phenyl sulfonates 5.6% diatomite 1.1% kaolin 7.4%

Suspension characteristics of the granulated product: 1 min / 0.01 ml; 5 min / 0.03 mL; 10 min / 0.04 mL.

Example 9b

Granulated product containing phenmedipham and ethofumesate

mice are prepared by plate granulation starting from the following mixture: (% =% by weight) phenmedifam 35.0% ethofumesate 34.7% lignosulfonates 5.9% phenyl sulfonates 5.6% diatomite 2.0% kaolin 16,8%

Suspension characteristics of the granulated product: 1 minute / 0.15 ml; 5 min / 0.5 ml; 10 min / 0.8 mL.

Example 10

Phenmedipham and Metamitron containing granulated terA granulated product suspension characteristics: 1 minute / 0.03 ml; 5 min / 0.10 mL; 10 min / 0.15 mL.

Example 12

Phenmedipham, Desmedipham and Chloridazone containing granulated product are prepared by plate granulation starting from the following mixture:

(% = by weight) Phenmedipham 12.0% Desmedipham 3.0% Chloridazone 45.0% Lignin sulfonates 5.9% Phenylsulfonates 7.0% Fluorinated surfactant 2.0% Alkylaryl betaine 5.0% Diatomaceous earth 1.0% lost 19.1%

meats are prepared by plate granulation starting from the following mixture: (% =% by weight) phenmedifam 16.0% methamitron 64.0% lignosulfonates 5.9% phenyl sulfonates 5.6% diatomite 2.0% kaolin 6.5%

Suspension characteristics of the granulated product: 1 min / 0.01 ml; 5 min / 0.02 mL; 10 min / 0.03 mL.

Suspension characteristics of the granulated product:

min / 0.1 ml; 5 min / 0.35 mL; 10 min / 0.45 mL.

Example 13

Phenmedipham and activator-containing tablets are prepared by applying a compression pressure of 300 kg / cm ² (Pa ³ -10 ⁷ ) starting from the following mixture:

(% = by weight) Phenmedipham 24.0% Lignin sulfonates 5.9% Phenylsulfonates 3.0% Sodium sulfonates 4.5% Potassium hydrogen phosphate 6.0%

HU 213 638 Β

Sodium carbonate 5.0% magnesium stearate 1.0% C mixture 50.0% kaolin 0.6%

The tablet is compressed in a 50 mL diameter form, using 30 g of blend in each form.

The suspension characteristics of the tablet are medium, if the dispersion of the tablet is suspended in a 500 ml decanter containing 300 ml of water and the suspension characteristics are visually checked.

Biological experiments:

The activity of the formulations prepared above is tested for their activity against weeds commonly found in the cultivated areas of sugar beet. Weeds include hairy hogweed (Amaranthus retroflexus), wild rape (Brassica napus), libatop (Chenopodium album) and hen (Stellaria media). Four planted pots per weed were used in the experiments. The efficacy of the preparation is given in the usual manner using a scale of 0 to 10, where the total kill of the plant is represented by 10. The average of the four parallel pot experiments is reported.

Damage to the sugar beet (Beta vulgaris) plant is also determined and reported on the above scale.

Experiment 1

The biological efficacy of a mixture of granulated phenmedipham (Example 1) and granular activator (Example 4) was compared with that of a commercially available phenmedipham-containing emulsion concentrate formulation (Kemifam) (Hoechst Schering AGREVO) (DE). The application rate for test weeds is the same, using 640 g of active ingredient per hectare. The efficacy of the active ingredient is evaluated on day 7 after spraying.

authorities material Efficacy I turn / hectare diszó- the grass on prosecution- rape pigweed hen- string sugar -carrot Kemi- fam 41 5.7 7.8 9.8 7.0 1.0 First example 0.8 kg 0.7 0.0 0.0 3.0 0.0 First EXAMPLE + 0.8 kg 4.0 8.0 8.3 7.7 0.3 4th example 1.5 kg First EXAMPLE + 0.8 kg 7.3 8.2 8.7 7.2 1.0 4th example 3.0 kg

The result shows that the granulated phenmedipham product is not biologically active without an activator. On the other hand, when a granular activator is used, the granulated phenmedipham product is activated such that the same product (3.8 kg compared to 4 liters of reference material) has better activity against the reference material and against the sugar beet as against the reference material. its effect is very low.

Experiment 2

The experiment compares the efficacy of granulated products containing phenmedipham and activator with the commercially available emulsion concentrate product (Kemifam) and the commercially available suspension concentrate product (Betaflow). The application rate per hectare is 640 g / ha in all experiments. The efficacy test is evaluated on the 14th day after spraying.

Test- test compound Efficacy pig- the grass on charlock chickweed sugar beet Kemifam 4 4 4 1 Betaflow 4 4 3 1 Example 5 3 3 4 1 Example 6 4 3 3 1

The results show that the biological activity of phenmedipham granulated formulations is the same as that of the emulsion or suspension concentrate reference materials. The adverse effect on the crop is also the same as that of the references.

Experiment 3

The experiment compares the effect of Example 8 Phenmedipham (69%) and Desmedipham (20%) granules with the Example 4 activator granule blend product on a commercially available emulsion concentrate formulation of 129 g / L phenmedipham and 34 mg / L phenmedipham. Contains g / l desmedipham. The amount of active ingredient per hectare was 652 g for Beta Compact and 640 g for the mixture of Example 8 + Example 4. The efficacy of the substances is determined on the 14th day after spraying.

Test compound Efficacy product/ hectare diszó- the grass on prosecution- rape pigweed chickweed sugar- carrot con com- pact 41 5.5 7.2 7.0 19.7 Shoot 8th example 0.8 kg 8.3 5.3 9.0 22.6 1.0 4th example 3.8 kg

The experiment shows that a mixture of phenmedipham and desmedipham is more potent than the corresponding emulsions8.

HU 213 638 Β concentrate product used as reference. The damage to sugar beet is the same for both products.

Experiment 4

The experiment compares the effect of the granulate formulation of Example 9, which is phenmedipham and ethofumesate, and the formulation of Example 4, which contains an activator, with the action of a commercially available emulsion concentrate, Betaron (HOECHST SCHERING AGREVO) (DE). 1 liter of phenmedipham and 100 g / liter of ethofumesate. The efficacy of the products was measured on the 14th day after spraying. The total amount of active substance used is 640 g / ha.

Test compound Effectiveness product/ hectare disznópa- pigweed charlock chickweed sugar- carrot observe 3.6 l 5 6 9 1 9b. example 0.81 kg 4 5 8 1 9b. EXAMPLE + 0.81 kg 8 7 8 1 4th example 0.67 kg

The experiment shows that a mixture of phenmedipham and ethofumesate also requires the addition of an activator, but in this case at least the same biological activity as that of the reference product can be achieved. The crop damage caused by the two formulations is the same.

Experiment 5

The experiment compares the effect of a mixture of the granulate product of Example 10, which contains phenmedipham and methamitrone, with the same product (Example 10) and the granule of Example 4, which contains an activator, to the action of the tank mix formulation, liters of active ingredient containing phenmedipham and a granular metamitron product (Goltix) at a concentration of 700 g / kg. The amount of active substance per hectare is the same for all tests. Efficacy was measured on the 14th day after spraying.

Test chemical being Efficacy product/ hectare disznópa- pigweed charlock chickweed sugar- carrot fenmedi- fam 1.5 1 9.5 9.5 10 01 SC Goltix 1.37 kg 10th example 1.5 kg 7.0 7.0 9.0 0

Test chemical being Efficacy product/ hectare disznópa- pigweed charlock chickweed sugar- carrot 10th EXAMPLE + 1.5 kg 7.0 9.0 9.5 0 4th example 1.1 kg

Metamitron, which can be applied to soil or foliage, does not require the use of activators as is required for phenmedipham; this is shown by the high potency of the granular product at 10. The use of phenmedipham + metamitron + activator granulated product provides excellent selective biological activity without any damage to sugar beet.

Experiment 6

The experiment compares the effect of the granulated product of Example 11b containing phenmedipham and chlorideazone, in which the concentration of the components is 20% and 60%, respectively, with the effect of the above granulated formulation and granulated activator, which is a mixture of as an active ingredient in a suspension concentrate product containing phenmedipham or chloridazone at concentrations of 100 g / l and 300 g / l, respectively. On the other hand, we investigate the importance of the activates in a ternary granular product, which contains the active ingredient phenmedipham, desmethpham and chlorideazone. The amount of active ingredient applied per hectare is the same in all experiments. The efficacy of the products is determined on the 14th day after spraying.

Test- Efficacy test compound product/ hectare pigweed disznópa- pigweed charlock sugar- carrot fenmedi- fam 4.81 6.0 8.0 8.0 0 SC klorida- zon 11b. example 2.4 kg 5.0 4.0 3.0 0 11b. EXAMPLE + 2.4 kg 6.0 6.0 7.0 0 4th example 2.3 kg 12th example 3.2 kg 7.0 6.0 5.0 1.0 12th EXAMPLE + 3.2 kg 9.0 6.0 7.5 1.0 4th example 2.3 kg

The results of the experiments show how the efficacy in the mixture composition increases

EN 213 638 Β phenmedipham on foliage and chlorideazone on soil. The same applies to the ternary mixture, which contains foliar desmedipham in addition to the two former active ingredients.

Field experiments

Field 1 Experiment

The purpose of the experiment is to compare the biological activity of phenmedipham-containing granular products with that of commercially available emulsion and suspension concentrate products.

The experiments are carried out according to the usual experimental procedure. The treatment is done 3 times, all treatments are done after the sugar beet has emerged. The efficacy of the products is determined visually by comparing the cultivated area of an untreated plant. Values in the untreated area are taken as 0. A value of 100 indicates perfect destruction. The amount of phenmedipham used in each treatment was 480 g / ha.

Test test! compound product / ha efficacy% 1.) Kemifam (phenmedipham 160 g / l, EC) 3 * 3 1 75 2.) Beta plus (Phenmedipham 16 g / L, SC) 3 * 3 1 83 3.) Example 1 + 3 * 0.6 kg 83 Example 4 3 * 1.15 kg 4.) Example 1 + 3 * 0.6 kg 93 Example 4 3 * 2.3 kg 5) Example 1 + 3 * 0.6 kg 83 Example 4 The mixture 3 * 1.4 kg 6) Example 7 3 * 1.5 kg 55 7) Example 7 + 3 * 1.5 kg 81 Example 4 3 * 1.15 kg

A granular product containing the active ingredient and a granular activator together with it at a total application rate of 1.75 kg / ha is as good as the suspension product when applied at a rate of 3 liters / ha. By using a granular product containing a greater amount of activator, in which case the total amount of material used is 2.57 kg / hectare, the granular product can be significantly more effective than the slurry product. In the experiments, the granules containing the activator are dispersed separately due to the assay technology, however, it is also possible to mix the granules containing the active ingredient and the activator together into a homogeneous mixture and then to disperse as a single mixture.

Liquid activators may also be used together with the active ingredient granular product in the form of a conventional tank mix, as was done in Test 5. The activator granule of Example 4 is

It contains 60% of the mixture and Experiments 4 and 5 contain equal amounts of the liquid component. However, it has been surprisingly found that the solid carrier of the granular product increases the activity of the activator granulate and in this case the efficacy of the active ingredient can be increased by up to 10%. It is also noteworthy that such a granular product is more than 10% more active than the suspension concentrate commercial product and up to 20% more active than the commercial emulsion concentrate product.

2. field trial

In this experiment, the effect of a product containing phenmedipham and etofumesate (Example 9a) granulated product and activator (Example 4) was compared with that of a commercially available emulsion concentrate product (Betaron). The test assay is performed as a field test of Experiment 1. The amount of active ingredient in each test was 540 g / ha.

I would do a test test product / ha efficacy% 1.) Betaron (Phenmedipham 80 g / L + Ethofumesate 100 g / L 3 * 31 95 2.) 9a. EXAMPLE + 3 * 0.75 kg 91 Example 4 3 * 0.58 kg 3) 9a. EXAMPLE + 0 * 0.75 kg 93 Example 4 3 * 1.15 kg

With a total amount of 1.33 kg of granular product, almost as effective a treatment as 3 liters of emulsion concentrate can be achieved. There is no difficulty in treating the product containing the active ingredient and the activator during spraying.

3. field experiment

The experiment compares the effectiveness of a spray program commonly used in sugar beet cultivation with that of a granulate spray program. In practice, phenmedipham, metamitron or ethofumesate are not used alone but in tank mixes. The proportion of each active ingredient in these tank mixes may vary depending on the weed.

Kemiron (HOECHST SCHEIZING AGREVO) (DE) is an emulsion concentrate containing 20 g / l etofumesate, granulated ethofumesate (EFU granulate) (Schering AG) (DE), a water dispersible granular product containing 65% of the active ingredient. The amount applied per hectare of active substance is the same for both studies and for both substances.

Usually used program:

Spray 1 1.5 L Kemifam + 1 kg Goltix + 0.5 L Kemiron

Spray 2 1.5 L Kemifan + 1 kg Goltix + 1.0 L Kemiron

Spray 3 1.5 L Kemifam + 0.5 kg Goltix + 1.0 L Kemiron

Spraying program based on granules:

HU213 638 Β

Spray 1 0.2 kg of the product of Example 1 + 1 kg Goltix + 1.15 kg EFU granules

Spray 2 0.2 kg product of Example 1 + 1 kg Goltix + 0.3 kg EFU granulate

Spray 3 0.2 kg Product of Example 1 + 0.5 kg Goltix + 0.3 kg EFU Granulate Material used for each spray 1.15 kg

Contains the product of Example 4.

Effectiveness: commonly used program 90% granulate based program 89%

The results show that a spraying program based on granular products is as effective as a spraying program using the active ingredient phenmedipham and ethofumesate in liquid form as an emulsion concentrate.

Claims (12)

PATENT CLAIMS CLAIMS 1. A process for the preparation of a granular herbicide composition comprising methyl [3- (m-tolylcarbamoyloxy) phenyl] carbamate or ethyl [3- (phenylcarbamoyloxy) phenyl] carbamate as an active ingredient. containing as surfactants and / or oils, the active ingredient being admixed with a solid carrier to form a solid activator composition to form a herbicidal composition comprising two separate solid phases and the product being obtained according to the following procedure. (a) preparing a granulate composition containing the herbicidal active ingredient and coating the granulate with a solid activator composition; or b) preparing a granulate comprising a solid activator composition and coating the granulate with a solid phase containing the herbicide; or c) first preparing a granulate composition containing the herbicidal active ingredient, second preparing a granule containing a solid activator composition and mixing the first and second granules. 2. The process of claim 1 wherein the activator component is a liquid material which is impregnated into a solid support. 3. The process of claim 2 wherein the activator component is a solid which is admixed with the solid support. 4. The process of claim 1 wherein the carrier is a material of natural origin. 5. The process of claim 1, wherein the carrier is a synthetic material. 6. A process according to claim 1, wherein the activator component is anionic, cationic, amphoteric or nonionic surfactants or mixtures thereof. The process according to claim 1, wherein the activator component is mineral oils, vegetable oils, animal oils, hydrolytic products or mixtures thereof. 8. The process of claim 1, wherein the surfactants are present in an amount of from 50% to 100% by weight of the activator. 9. The process of claim 1, wherein the oil is present in an amount of up to 50% by weight of the activator. 10. The process of claim 1, wherein the activator is present in an amount of from 10 to 70% by weight of the activator solid composition. 11. The process of claim 1, wherein the activator composition comprises excipients suitable for dispersing, wetting, granulating, stabilizing, adjusting the pH, or inhibiting foaming of the activator composition. 12. The process according to claim 1, wherein, in addition to the herbicide active ingredients used above, other plant protection agents such as chloridazone, methamitrone or ethofumesate are used in the composition in the same granules as the herbicide active ingredient or in separate granules. used.